Powdered preparations containing a mixture of 2,4,6-trianilino-p-(carbo-2&#39;-ethylhexyl-1&#39;-oxi)-1,3,5-triazine and diethylamino-hydroxybenzoyl-hexyl-benzoate

ABSTRACT

The invention relates to a method of producing powdered preparations comprising 2,4,6 trianilino p (carbo 2′-ethylexyl-1′-oxy)-1,3,5 triazine of the formula I  
                 
 
and diethylamino hydroxybenzoyl hexyl benzoate of the formula II  
                 
the method comprising: a) jointly dispersing the compounds I and II in an aqueous molecularly disperse or colloidally disperse solution of a protective colloid; and b) converting the dispersion obtained into a dry powder by removing the water and drying, wherein the protective colloid used in process step a) is modified starch.

The invention relates to powdered preparations comprising a mixture of2,4,6-trianilino-p-(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine anddiethylamino hydroxybenzoyl hexyl benzoate, to their preparation and tothe use thereof as photoprotective agents.

The quality and life span of many organic materials, for exampleplastics and coating materials, but also pharmaceutical and cosmeticpreparations, can be adversely affected by the action of light, inparticular by UV rays. These losses in quality frequently become evidentin the case of plastics and coating materials from yellowing,discoloration, cracking or embrittlement of the material. In the case ofpharmaceutical and cosmetic preparations, the effect of UV rays can leadto the degradation of the active ingredients present in theformulations.

The harmful effect of the ultraviolet part of solar radiation on theskin or hair, which in the widest sense are also an organic material, islikewise a problem which is increasing in importance. While rays havinga wavelength of less than 290 nm (the UVC region) are absorbed by theozone layer in the earth's atmosphere, rays in the range between 290 nmand 320 nm, the UVB region, cause an erythema, simple sunburn or evenburns of varying severity on the skin.

A maximum for the erythema activity of sunlight is given as therelatively narrow range around 308 nm.

Numerous compounds are known for protecting against UVB radiation; theseare, inter alia, triazine derivatives, derivatives of3-benzylidenecamphor, of 4-aminobenzoic acid, of cinnamic acid, ofsalicylic acid, of benzophenone and of 2-phenylbenzimidazole.

It is also important to have available filter substances for the rangebetween about 320 nm and about 400 nm, the UVA region, since its rayscan cause reactions in cases of photosensitive skin. It has been proventhat UVA radiation leads to damage of the elastic and collagenous fibersof the connective tissue, leading to premature aging of the skin, andthat it is to be regarded as a cause of numerous phototoxic andphotoallergic reactions. The harmful effect of UVB radiation can beintensified by UVA radiation.

To protect against UVA rays, derivatives of dibenzoylmethane are used,the photostability of which, however, is inadequate (Int. J. Cosm.Science 10, 53 (1988)).

EP-A-1 046 391 describes the use of aminosubstitutedhydroxybenzophenones as photostable UVA filters in cosmeticpreparations.

However, UV radiation can also lead to photochemical reactions, in whichcase the photochemical reaction products then intervene in the skin'smetabolism.

Such photochemical reaction products are mainly free-radical compounds,for example hydroxyl radicals. Undefined free-radical photo productsformed in the skin itself can also trigger uncontrolled secondaryreactions as a result of their high reactivity. However, singlet oxygen,a non-radical excited state of the oxygen molecule, can also ariseduring UV irradiation, as can short-lived epoxides and many others.Singlet oxygen, for example, differs from normal triplet oxygen(free-radical ground state) by virtue of its increased reactivity.However, activated, reactive (free-radical) triplet states of the oxygenmolecule also exist.

Furthermore, UV radiation is a form of ionizing radiation. There istherefore the risk that ionic species will also form during UV exposure,which then for their part are able to intervene oxidatively in thebiochemical processes.

One applications-relevant disadvantage of many UV filters is their poorsolubility in water and/or in natural and synthetic oils, for example insilicone oils and in fatty acid triglycerides, as a result of whichtheir use, for example in cosmetic formulations, is often restricted.

A further disadvantage associated with the application of somephotoprotective agents is the appearance of skin irritations andallergies resulting from too high a skin permeability.

Numerous methods have already been published for improving theformulation properties of insoluble or only sparingly soluble UVabsorbers.

For example, GB-A-2 303 549 describes a grinding process for thepreparation of micronized insoluble organic UV absorbers in the presenceof alkyl polyglycosides. The resulting micronizates can be incorporatedinto cosmetic photoprotective preparations.

GB-A-2 286 774 likewise describes a grinding process for themicronization of insoluble organic UV absorbers.

EP-A-1 127 567 describes aqueous dispersions of sparingly water-solubleor water-insoluble organic UV filter substances and dry powders producedtherefrom, wherein they comprise at least one sparingly water-soluble orwater-insoluble organic UV filter substance as colloidally dispersephase in amorphous of partially amorphous form. The use of theprotective colloids specified in this specification—in particulargelatin or casein or caseinate—leads to powdered products whosesolubility in cold water is unsatisfactory. In addition, gelatin andcasein in cosmetic formulations can cause skin allergies.

It was then an object of the present invention to provide a method ofproducing photoprotective agent formulations which offer effectiveprotection for organic material, in particular for the human skin and/orhuman hair, against UVA and UVB rays, which are well tolerated by theskin and which can be incorporated easily both into lipophilic and alsoin particular into aqueous systems.

This object was achieved by a method of producing powdered preparationscomprising 2,4,6-trianilino(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazineof the formula I

and diethylamino hydroxybenzoyl hexyl benzoate of the formula II

by

-   a) jointly dispersing the compounds I and II in an aqueous    molecularly disperse or colloidally disperse solution of a    protective colloid and-   b) converting the dispersion obtained into a dry powder by removing    the water and, if appropriate, additionally used solvents, and    drying,    wherein the protective colloid used in process step a) is modified    starch.

2,4,6-Trianilino-p-(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine of theformula I is marketed by BASF Aktiengesellschaft under the tradenameUvinul

T150 as a UVB filter. Uvinul

T150 is notable, inter alia, for good UV absorption properties with anexceptionally high absorbance coefficient>1500 at 314 nm.

Diethylamino hydroxybenzoyl hexyl benzoate of the formula II is marketedby BASF Aktiengesellschaft under the trade name Uvinul® A Plus as a UVAfilter. Uvinul® A Plus is notable, inter alia, for high photostabilityand good UV absorption properties with a high absorbance coefficient of940 at 354 nm.

For the purposes of the present invention, the term aqueous dispersionsis understood as meaning both aqueous suspensions and emulsions.Preferred aqueous suspensions which may be mentioned are those in whichthe disperse phase comprises the triazine I and the benzoyl benzoate IIas nanoparticulate particles.

For the purposes of the present invention, the term modified starchpreferably comprises esters of starch with organic acids, e.g. withacetic acid and higher fatty acids (C₆-C₂₆), and with succinic acid,adipic acid and citric acid. The starch can be obtained here, interalia, from corn, potatoes or wheat. A particularly preferred modifiedstarch is octenyl succinate starch, which is marketed under the tradename HiCap® by National Starch or EmCap® by Cerestar.

A preferred variant of the method according to the invention is one inwhich the dispersion in stage a) comprises the following steps:

-   a₁) dissolving the compounds I and II in one or more water-miscible    organic solvent(s) or in a mixture of water and one or more    water-miscible organic solvent(s) or-   a₂) dissolving the compounds I and II in one or more    water-immiscible organic solvent(s) and-   a₃) mixing the solution obtained after a₁) or a₂) with an aqueous    molecularly disperse or colloidally disperse solution of modified    starch, where the hydrophobic phase of the triazine I is formed as    nanodisperse phase.

Depending on the type of solvent used, the nanodisperse phase in stepa₃) may be solid nanoparticles [suspension; obtainable by combining a₁)and a₃)] or nanodroplets [emulsion; obtainable by combining a₂) anda₃)].

The water-miscible solvents used in stage a₁) are primarilywater-miscible, thermally stable, volatile solvents comprising onlycarbon, hydrogen and oxygen, such as alcohols, ethers, esters, ketonesand acetals. It is expedient to use those solvents which are at least10% water-miscible, have a boiling point below 200° C., preferably below100° C., and/or have fewer than 10 carbons. Particular preference isgiven to methanol, ethanol, n-propanol, isopropanol, 1,2-butanediol1-methyl ether, 1,2-propanediol 1-n-propyl ether, tetrahydrofuran oracetone or mixtures thereof, and very particular preference is given tousing isopropanol or acetone.

For the purposes of the present invention, the term “a water-immiscibleorganic solvent” is an organic solvent with a solubility in water atatmospheric pressure of less than 10%. Suitable possible solvents hereare, inter alia, halogenated aliphatic hydrocarbons, such as, forexample, methylene chloride, chloroform or carbon tetrachloride,carboxylic acid esters, such as diethyl carbonate, ethyl formate,methyl, ethyl or isopropyl acetate, and ethers, such as methyltert-butyl ether. Preferred water-immiscible organic solvents are thefollowing compounds from the group consisting of dimethyl carbonate,propylene carbonate, ethyl formate, ethyl acetate, isopropyl acetate andmethyl tert-butyl ether.

The dry powder in process step b) can be produced here, inter alia, byspray-drying, spray-cooling, freeze-drying, and by drying in a fluidizedbed, convention drying or contact drying, it also being possible tocarry out the drying in the presence of a coating material (powderingagent). Suitable coating agents are, inter alia, corn starch, silica andalso tricalcium phosphate.

During the lyophilization of the nanoparticles according to theinvention, cryoprotective substances such as, for example, trehalose orpolyvinylpyrrolidones, can be added to the nanoparticles according tothe invention.

Particular preference is given to an embodiment of the method accordingto the invention in which

-   a₁) the compounds I and II are dissolved in acetone or isopropanol    or a mixture of water and acetone or water and isopropanol at    temperatures in the range from 50 to 240° C.,-   a₃) the solution obtained is mixed with an aqueous molecularly    disperse or colloidally disperse solution of modified starch, in    particular octenyl succinate starch, at temperatures in the range    from 25 to 120° C. and-   b) the suspension formed is spray-dried after removing the organic    solvent.

The abovementioned dry powders are advantageously produced by jointlydissolving the compounds I and II in acetone or isopropanol or a mixtureof water and acetone or water and isopropanol at temperatures in therange from 50° C. to 240° C., in particular 100° C. to 200° C.,particularly preferably in the range from 105° C. to 180° C.

To produce the molecularly disperse solution rapidly, the application ofincreased pressure, e.g. in the range from 20 bar to 80 200 bar,preferably 30 to 100 bar, may be advantageous.

The molecularly disperse solution obtained in this way is then mixeddirectly with the, if appropriate cooled, aqueous molecularly disperseor colloidally disperse solution of the modified starch, in particularoctenyl succinate starch, in such a way that a mixing temperature ofabout 25° C. to 120° C., preferably 40° C. to 80° C., particularlypreferably 45° C. to 70° C., is established.

In so doing, the solvent component is converted into the aqueous phaseand the hydrophobic phase of the triazine I and of the benzoyl benzoateII is formed as nanodisperse phase.

The mixing in step a₃) can be carried out by initially introducing thesolution comprising triazine and benzoyl benzoate, and metering in theaqueous solution of modified starch, or vice versa, or preferably bymetering in both solutions simultaneously and continuously into a mixingchamber.

With regard to a more detailed description of the method and apparatusrelating to the abovementioned dispersion, reference is made at thispoint to EP-B-0 065 193.

To increase the mechanical stability of the end product, in some casesit may be advantageous to add a further plasticizer to the colloid, suchas sugars or sugar alcohols, e.g. sucrose, glucose, glucose syrup,dextrin, inverted sugar, sorbitol, mannitol or glycerol.

To increase the stability of the active ingredient against oxidativedegradation, it may likewise be expedient to add stabilizers such asα-tocopherol, t-butylhydroxytoluene, t-butylhydroxyanisole, ascorbicacid or ethoxyquin. They can either be added to the aqueous phase or tothe solvent phase, although they are preferably dissolved together withthe triazine I in the solvent phase.

In addition, the photoprotective agent formulations can comprise lowmolecular weight surface-active compounds (emulsifiers) in aconcentration of from 0.01 to 70% by weight, preferably 0.1 to 50% byweight, particularly preferably 0.5 to 20% by weight, based on the drymass of the photoprotective agent formulation. Suitable as such areprimarily amphiphilic compounds or mixtures of such compounds. Inprinciple, all surfactants with an HLB value of from 5 to 20 aresuitable. Suitable corresponding surface-active substances are, forexample: esters of long-chain fatty acids with ascorbic acid, mono- anddiglycerides of fatty acids and oxymethylation products thereof, estersof monofatty acid glycerides with acetic acid, citric acid, lactic acidor diacetyltartaric acid, polyglycerol fatty acid esters, such as, forexample, the monostearate of triglycerol, sorbitan fatty acid esters,propylene glycol fatty acid esters and lecithin. Preference is given tousing ascorbyl palmitate.

To increase the stability of the active ingredient against microbialdegradation, it may be expedient to add preservatives to thepreparation, such as, for example, methyl 4-hydroxybenzoate, propyl4-hydroxybenzoate, sorbic acid or benzoic acid or salts thereof.

According to the invention, dry powders can thus be obtained which nolonger lose their properties obtained in the primary dispersion. Thismeans that the amorphous or partially crystalline character of the UVfilter substances I and II is retained. It is also a property accordingto the invention that these powders, upon redispersion, have the sameparticle size distribution which they had as primary dispersion with adeviation of 20%, preferably <15%. It is likewise advantageous that thedry powders according to the invention absorb both in the UVA and in theUVB region.

A further preferred embodiment of the abovementioned method is one inwhich the suspension prepared in process step a) is ground before beingconverted into a dry powder.

The grinding method is preferably carried out by jointly suspending thetriazine I and the benzoyl benzoate 11 in crystalline form in an aqueousmoleculariy disperse or colloidally disperse solution of modifiedstarch, and comminuting to the desired particle size by grinding.

The grinding can be carried out here in a manner known per se, e.g.using a ball mill. Depending on the type of mill used, grinding iscarried out until the particles have an average particle size,determined via Fraunhofer diffraction, D[4.3] of from 0.01 to 100 μm,preferably from 0.02 to 50 μm, particularly preferably 0.05 to 20 μm,very particularly preferably 0.05 to 5 μm, in particular 0.1 to 1 μm.The term D[4.3] refers to the volume-weighted average diameter (seehandbook for Malvern Mastersizer S, Malvem Instruments Ltd., UK).

By heating the aqueous suspension after the grinding process to atemperature above the melting point of the triazine I and of the benzoylbenzoate II and then spray-drying the “melt emulsion”, it is possible toincrease the amorphous fraction of the active ingredients I and II inthe resulting dry powder. Details regarding the grinding of activeingredients in aqueous protective colloid solutions are given in EP-B-0498 824 and EP-B-0 684 973.

The invention also provides powdered preparations of a mixture of2,4,6-trianilino-p-(carbo -2′-ethylhexyl-1′-oxy)-1,3,5-triazine of theformula I and diethylamino hydroxybenzoyl hexyl benzoate of the formulaII obtainable by the abovementioned methods.

The novel photoprotective agent formulations are notable for the factthat they comprise the compounds I and II, the amorphous fraction ofwhich is in the range greater than 10%, preferably greater than 30%,particularly preferably in the range from 50 to 100%, very particularlypreferably in the range from 75 to 99%. The degrees of crystallinity ofthe active ingredients I and II can be determined here, for example, byX-ray diffraction measurements.

The content of UV absorbers of the formulae I and II in thephotoprotective agent formulations according to the invention is in therange from 0.1 to 70% by weight, preferably in the range from 2 to 40%by weight, particularly preferably in the range from 3 to 30% by weight,very particularly preferably in the range from 5 to 25% by weight, basedon the dry mass of the formulations.

Per part by weight of triazine of the formula I, the photoprotectiveagent formulations according to the invention comprise 0.1 to 10 partsby weight of benzoyl benzoate of the formula II, preferably 0.5 to 2parts by weight, particularly preferably 0.8 to 1.2 parts by weight, ofbenzoyl benzoate of the formula II.

The average particle size D[4.3] of the nanoparticulate particles in theaqueous dispersion is, depending on the formulation method, in the rangefrom 0.01 to 100 μm, preferably in the range from 0.02 to 50 μm,particularly preferably in the range from 0.05 to 20 μm, veryparticularly preferably in the range from 0.05 to 5 μm, in particular0.1 to 1 μm.

Whereas ground UV filter substances, when incorporated into skin creams,have an increased propensity for particle size growth, which can lead toa deterioration of the sun protection factor and to an unpleasant feelon the skin, the dry powders according to the invention do not have suchtendencies on account of their matrix and protective colloid structure.

The formulations according to the invention—dispersions and dry powdersprepared therefrom—are highly suitable for stabilizing organic materialinter alia against the effect of light, oxygen and heat. They are addedto the organic material to be stabilized in a concentration of from 0.01to 10% by weight, preferably 0.01 to 5% by weight, particularlypreferably from 0.02 to 2% by weight, based on the organic material,before, during or after its preparation.

Organic material is understood as meaning, for example, photographicrecording materials, in particular photographic emulsions or precursorsfor plastics and surface coatings, but in particular plastics andsurface coatings themselves.

Organic material, however, also means cosmetic preparations, such as,for example, creams, lotions, gels, lipsticks.

The present invention further relates to organic material stabilizedagainst the action of light, oxygen and heat, in particular plastics andsurface coatings, comprising 0.01 to 10% by weight, preferably 0.01 to5% by weight, particularly preferably from 0.02 to 2% by weight, basedon the total amount of the organic material, of the compounds I and IIin the form of the formulations according to the invention.

For mixing the formulations according to the invention primarily withplastics, it is possible to use all known devices and methods for mixingstabilizing agents or other additives into polymers.

The organic material stabilized by the formulations according to theinvention can, if appropriate, comprise further additives, e.g.antioxidants, light stabilizing agents, metal deactivators, antistaticagents, flame retardants, pigments and fillers.

Antioxidants and light stabilizers which can be added in addition to theformulations according to the invention are, for example, compoundsbased on sterically hindered phenols or costabilizers comprising sulfuror phosphorus.

Examples of such phenolic antioxidants are2,6-di-tert-butyl-4-methylphenol,n-octadecyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylethyl]isocyanurate,1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate andpentaerythritoltetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

Examples of suitable phosphorus-comprising antioxidants aretris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl)phosphite,tris(2-tert-butyl-4-methylphenyl)phosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite andtetrakis(2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphite.

Examples of sulfur-comprising antioxidants are dilaurylthiodipropionate, dimyristyl thiodipropionate, distearylthiodipropionate, pentaerythritol tetrakis(β-laurylthiopropionate) andpentaerythritol tetrakis-(β-hexylthiopropionate).

Other antioxidants and light stabilizers which can be used together withthe formulations according to the invention are, for example,2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, aryl estersof hydroxybenzoic acids, α-cyanocinnamic acid derivatives,benzimidazolecarboxanilides, nickel compounds or oxalanilides.

Particularly good stabilization is achieved when at least one lightstabilizer from the compound class of sterically hindered amines is alsoadded in the usual concentration to the formulations according to theinvention.

Examples of suitable sterically hindered amines are:bis(2,2,6,6-tetramethylpiperidyl) sebacate,bis(1,2,2,6,6-pentamethylpiperidyl)sebacate, the condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensation product ofN,N′-di(2,2,6,6-tetramethylpiperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethylpiperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), thecondensation products of 4-amino-2,2,6,6-tetramethylpiperidines andtetramethylolacetylenediureas.

Examples of plastics which can be stabilized by the compounds Iaccording to the invention and may be mentioned are:

polymers of mono- and diolefins, such as, for example, low density orhigh density polyethylene, polypropylene, linear poly-1-butene,polyisoprene, polybutadiene, and copolymers of mono- or diolefins ormixtures of said polymers;

copolymers of mono- or diolefins with other vinyl monomers, such as, forexample, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers;

polystyrene and copolymers of styrene or -α-methylstyrene with dienesand/or acrylic derivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile (SAN), styrene/ethyl methacrylate,styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methacrylate,acrylonitrile/butadiene/styrene (ABS) or methylmethacrylate/butadiene/styrene (MBS);

halogen-containing polymers, such as, for example, polyvinyl chloride,polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof;

polymers derived from α,β-unsaturated acids and derivatives thereof,such as polyacrylates, polymethacrylates, polyacrylamides andpolyacrylonitriles;

polymers derived from unsaturated alcohols and amines or acylderivatives or acetals thereof, e.g. polyvinyl alcohol and polyvinylacetate;

polyurethanes, polyamides, polyureas, polyesters, polycarbonates,polysulfonates, polyether sulfones and polyether ketones.

Furthermore, the formulations according to the invention can be used tostabilize aqueous emulsion paints and surface coatings, e.g. industrialfinishes. Of these, particular attention is drawn to baking finishes,and, in turn, of these, automotive finishes, preferably two-coatfinishes.

The formulations can be added in solid or liquid form to the surfacecoating. Their good solubility in surface coating systems is ofparticular advantage here.

Even in the case of the use as stabilizers in surface coatings, it ispossible also to use the additional additives already listed, inparticular antioxidants and light stabilizers.

The photoprotective agent formulations according to the invention arealso very particularly preferably suitable as photostable UV filters incosmetic and dermatological preparations for protecting human skin orhuman hair from solar rays and also from artificial light which has highUV contents, alone or together with compounds which absorb in the UVregion and are known for cosmetic or pharmaceutical preparations. Thus,in the widest sense, the term organic materials also means human skinand human hair. The cosmetic and pharmaceutical preparations as such areof course also stabilized at the same time in order to remain effectivefor as long as possible.

Accordingly, the present invention also relates to cosmetic andpharmaceutical preparations comprising photoprotective agents forprotecting human skin or human hair from UV light in the range from 280to 400 nm, which comprise, as photostable UV filters and in acosmetically or pharmaceutically suitable carrier, effective amounts ofa formulation of the compounds I and II in amorphous or partiallyamorphous form—alone or together with compounds which absorb in the UV-Aand UV-B region and are known per se for cosmetic and pharmaceuticalpreparations—the formulations being aqueous dispersions according to theinvention mentioned in the introduction or the dry powders preparedtherefrom.

The amount of triazine I and benzoyl benzoate II in the form of theformulations according to the invention which is used in the cosmeticand pharmaceutical preparations is in the range from 0.05 to 20% byweight, preferably 0.1 to 10% by weight, particularly preferably in therange from 1 to 7% by weight, based on the total amount of the cosmeticand pharmaceutical preparation.

The cosmetic and pharmaceutical preparations comprising photoprotectiveagents are generally based on a carrier which comprises at least one oilphase. Preparations based solely on aqueous components are, however,also possible. Accordingly, suitable preparations are oils, oil-in-waterand water-in-oil emulsions, creams and pastes, lip-protection stickcompositions or grease-free gels.

Suitable emulsions are inter alia also O/W macroemulsions, O/Wmicroemulsions or O/W/O emulsions containing compounds of the formula Iand II present in dispersed form, the emulsions being obtainable byphase inversion technology, as in DE-A-197 26 121.

Customary cosmetic auxiliaries which may be suitable as additives are,for example, coemulsifiers, fats and waxes, stabilizers, thickeners,biogenic active ingredients, film formers, fragrances, dyes, pearlizingagents, preservatives, pigments, electrolytes (e.g. magnesium sulfate)and pH regulators. Suitable coemulsifiers are, preferably, known W/O andalso O/W emulsifiers, such as, for example, polyglycerol esters,sorbitan esters or partially esterified glycerides. Typical examples offats are glycerides; waxes which may be mentioned are inter aliabeeswax, paraffin wax or microcrystalline waxes, if appropriate incombination with hydrophilic waxes. Stabilizers which may be used aremetal salts of fatty acids, such as, for example, magnesium, aluminumand/or zinc stearate. Examples of suitable thickeners are crosslinkedpolyacrylic acids and derivatives thereof, polysaccharides, inparticular xanthan gum, guar guar, agar agar, alginates and tyloses,carboxymethylcellulose and hydroxyethylcellulose, and also fattyalcohols, monoglycerides and fatty acids, polycrylates, polyvinylalcohol and polyvinylpyrrolidone. The term biogenic active ingredientsmeans, for example, plant extracts, protein hydrolyzates and vitamincomplexes. Customary film formers are, for example, hydrocolloids, suchas chitosan, microcrystalline chitosan or quaternary chitosan,polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymers,polymers of the acrylic acid series, quaternary cellulose derivativesand similar compounds. Examples of suitable preservatives areformaldehyde solution, p-hydroxybenzoate or sorbic acid. Examples ofsuitable pearlizing agents are glycol distearic esters, such as ethyleneglycol distearate, but also fatty acids and fatty acid monoglycolesters. Dyes which may be used are the substances suitable and approvedfor cosmetic purposes, as listed, for example, in the publication“Kosmetische Farbemittel” [Cosmetic Colorants] from theFarbstoffkommission der Deutschen Forschungsgemeinschaft [DyesCommission of the German Research Council], published by Verlag Chemie,Weinheim, 1984. These dyes are usually used in a concentration of from0.001 to 0.1% by weight, based on the total mixture.

An additional content of antioxidants is generally preferred. Thus,favorable antioxidants which can be used are all antioxidants which aresuitable or customary for cosmetic and/or dermatological applications.

The antioxidants are advantageously chosen from the group consisting ofamino acids (e.g. glycine, histidine, tyrosine, tryptophan) andderivatives thereof, imidazoles (e.g. urocanic acid) and derivativesthereof, peptides such as D,L-carnosine, D-camosine, L-camosine andderivatives thereof (e.g. anserine), carotenoids, carotene (e.g.β-carotene, lycopene) and derivatives thereof, chlorogenic acid andderivatives thereof, lipoic acid and derivatives thereof (e.g.dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols(e.g. thiorodoxin, glutathione, cysteine, cystine, cystamine and theglycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl,palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof)and salts thereof, dilauryl thiodipropionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof (esters,ethers, peptides, lipids, nucleotides, nucleosides and salts) andsulfoximine compounds (e.g. buthionine sulfoximines, homocysteinesulfoximines, buthionine sulfones, penta-, hexa-, heptathioninesulfoximine) in very low tolerated doses (e.g. pmol to pmol/kg), also(metal) chelating agents (e.g. α-hydroxyfatty acids, palmitic acid,phytic acid, lactoferrin), α-hydroxy acids (e.g. citric acid, lacticacid, malic acid), humic acid, bile acid, bile extracts, bilirubin,biliverdin, EDTA and derivatives thereof, unsaturated fatty acids andderivatives thereof (e.g. γ-linolenic acid, linoleic acid, oleic acid),folic acid and derivatives thereof, ubiquinone and ubiquinol andderivatives thereof, vitamin C and derivatives thereof (e.g. ascorbylpalmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherol andderivatives (e.g. vitamin E acetate, tocotrienol), vitamin A andderivatives (vitamin A palmitate) and coniferyl benzoate of benzoinresin, rutic acid and derivatives thereof, α-glycosylrutin, ferulicacid, furfurylideneglucitol, carnosine, butylhydroxytoluene,butylhydroxyanisole, nordihydroguaiac resin acid, nordihydroguaiareticacid, trihydroxybutyrophenone, uric acid and derivatives thereof,mannose and derivatives thereof, zinc and derivatives thereof (e.g. ZnO,ZnSO₄), selenium and derivatives thereof (e.g. selenomethionine),stilbenes and derivatives thereof (e.g. stilbene oxide, trans-stilbeneoxide).

The amount of the abovementioned antioxidants (one or more compounds) inthe preparations is preferably 0.001 to 30% by weight, particularlypreferably 0.05 to 20% by weight, in particular 1 to 10% by weight,based on the total weight of the preparation.

If vitamin E and/or derivatives thereof are the antioxidant orantioxidants, it is advantageous to choose the respective concentrationthereof from the range 0.001 to 10% by weight, based on the total weightof the formulation.

If vitamin A and/or derivatives thereof or carotenoids are theantioxidant or antioxidants, it is advantageous to choose the respectiveconcentration thereof from the range 0.001 to 10% by weight, based onthe total weight of the formulation.

Customary oil components in cosmetics are, for example, silicone oils,paraffin oil, glyceryl stearate, isopropyl myristate, diisopropyladipate, cetylstearyl 2-ethylhexanoate, hydrogenated polyisobutene,vaseline, caprylic/capric triglycerides, microcrystalline wax, lanolinand stearic acid.

The total proportion of auxiliaries and additives can be 1 to 80% byweight, preferably 6 to 40% by weight, and the nonaqueous proportion(“active substance”) can be 20 to 80% by weight, preferably 30 to 70% byweight, based on the compositions. The compositions can be prepared in amanner known per se, i.e. for example by hot, cold, hot-hot/cold or PITemulsification. This is a purely mechanical process, and no chemicalreaction takes place.

Such sunscreen preparations can accordingly be in liquid, paste or solidform, for example as water-in-oil creams, oil-in-water creams andlotions, aerosol foam creams, gels, oils, marking pencils, powders,sprays or alcohol-aqueous lotions.

Finally, it is possible additionally to use further substances known perse which absorb in the UV region, provided they are stable in theoverall system of the combination of UV filters to be used according tothe invention.

The majority of photoprotective agents in the cosmetic andpharmaceutical preparations used to protect the human epidermis consistsof compounds which absorb UV light in the UV-B region, i.e. in the rangefrom 280 to 320 nm. For example, the proportion of the UV-A absorbers tobe used according to the invention is 10 to 90% by weight, preferably 20to 50% by weight, based on the total amount of UV-B and UV-A absorbingsubstances.

Suitable UV filter substances which are used in combination with theformulations to be used according to the invention are any UV-A and UV-Bfilter substances. Examples which may be mentioned are: No Substance CASNo. (=acid) 1 4-Aminobenzoic acid 150-13-0 23-(4′-Trimethylammonium)benzylidenebornan-2-one 52793-97-2 methylsulfate3 3,3,5-Trimethylcyclohexyl salicylate(homosalate) 118-56-9 42-Hydroxy-4-methoxybenzophenone(oxybenzone) 131-57-7 52-Phenylbenzimidazole-5-sulfonic acid and its potassium, 27503-81-7sodium and triethanolamine salts 63,3′-(1,4-Phenylenedimethine)-bis(7,7-dimethyl-2- 90457-82-2oxobicyclo[2.2.1]heptane-1-methanesulfonic acid) and its salts 7Polyethoxyethyl 4-bis(polyethoxy)aminobenzoate 113010-52-9 82-Ethylhexyl 4-dimethylaminobenzoate 21245-02-3 9 2-Ethylhexylsalicylate 118-60-5 10 2-Isoamyl 4-methoxycinnamate 71617-10-2 112-Ethylhexyl 4-methoxycinnamate 5466-77-3 122-Hydroxy-4-methoxybenzophenone-5-sulfonicacid 4065-45-6 (sulisobenzone)and the sodium salt 13 3-(4′-Sulfobenzylidene)bornan-2-one and salts58030-58-6 14 3-Benzylidenebornan-2one 16087-24-8 151-(4′-Isopropylphenyl)-3-phenylpropane-1,3-dione 63260-25-9 164-Isopropylbenzyl salicylate 94134-93-7 17 3-Imidazol-4-ylacrylic acidand its ethyl ester 104-98-3 18 Ethyl 2-cyano-3,3-diphenylacrylate5232-99-5 19 2′-Ethylhexyl 2-cyano-3,3-diphenylacrylate 6197-30-4 20Menthyl o-aminobenzoate or:5-methyl-2-(1-methylethyl)-2- 134-09-8aminobenzoate 21 Glyceryl p-aminobenzoate or:1-glyceryl 4-aminobenzoate136-44-7 22 2,2′-Dihydroxy-4-methoxybenzophenone (dioxybenzone) 131-53-323 2-Hydroxy-4-methoxy-4-methylbenzophenone (mexenone) 1641-17-4 24Triethanolamine salicylate 2174-16-5 25 Dimethoxyphenylglyoxalic acid orsodium 3,4- 4732-70-1 dimethoxyphenylglyoxalate 263-(4′-Sulfobenzylidene)bornan-2-one and its salts 56039-58-8 274-tert-Butyl-4′-methoxydibenzoylmethane 70356-09-1 282,2′,4,4′-Tetrahydroxybenzophenone 131-55-5 292,2′-Methylenebis[6(2H-benzotriazol-2-yl)-4-(1,1,3,3- 103597-45-1tetramethylbutyl)phenol] 302,2′-(1,4-Phenylene)-bis-1H-benzimidazole-4,6-disulfonic 180898-37-7acid, Na salt 31 2,4-bis[4-(2-Ethylhexyloxy)-2-hydroxy]phenyl-6-(4-187393-00-6 methoxyphenyl)-(1,3,5)-triazine 323-(4-Methylbenzylidene)camphor 36861-47-9 33 Polyethoxyethyl4-bis(polyethoxy)paraaminobenzoate 113010-52-9 342,4-Dihydroxybenzophenone 131-56-6 352,2′-Dihydroxy-4,4′-dimethoxybenzophenone-5,5′-disodium 3121-60-6sulfonate

Polymeric or polymer-bonded filter substances can also be used accordingto the invention.

The cosmetic and dermatological preparations according to the inventioncan additionally advantageously comprise inorganic pigments based onmetal oxides and/or other metal compounds which are insoluble orsparingly soluble in water, for example the oxides of titanium (TiO₂),zinc (ZnO), iron (e.g. Fe₂O₃), zirconium (ZrO₂), silicon (SiO₂),manganese (e.g. MnO), aluminum (Al₂O₃), cerium (e.g. Ce₂O₃), mixedoxides of the corresponding metals, and mixtures of such oxides.Particular preference is given to pigments based on TiO₂ and ZnO.

The inorganic pigments may be present here in hydrophobic form, i.e.surface-treated to repel water. This surface treatment may involveproviding the pigments with a thin hydrophobic layer by a method knownper se, as described in DE-A-33 14 742.

To protect human hair from UV rays, the photoprotective agentformulations according to the invention can be incorporated intoshampoos, lotions, gels, hairsprays, hair colorants, aerosol foam creamsor emulsions in concentrations of from 0.1 to 10% by weight, preferably1 to 7% by weight. The respective formulations can inter alia be usedfor washing, coloring and for styling hair.

The formulations to be used according to the invention are usuallynotable for a particularly high absorbance in the UV-A radiation regionwith a sharp band structure. Moreover, they are readily soluble incosmetic oils and can easily be incorporated into cosmetic formulations.The emulsions prepared with the formulations are particularly notablefor their high stability, the formulations themselves are notable fortheir high photostability, and the preparations prepared therewith arenotable for their pleasant feel on the skin.

The UV filter action of the formulations according to the invention canalso be utilized for stabilizing active ingredients and auxiliaries incosmetic and pharmaceutical formulations.

The preparations according to the invention are notable for particularlyhigh absorbance in the UV-A and UV-B radiation region with a sharp bandstructure and high light protection factors.

In particular, the high sun protection factor of the preparations whichwas measured even at low concentrations of the UV-absorbing activeingredients I and II was surprising.

In addition, the preparations according to the invention have theadvantage over other triazihe-containing and benzoyl benzoate-containingformulations of improved dispersibility in cold water.

The examples below serve to illustrate the present invention withoutlimiting it.

EXAMPLE 1

Preparation of a Uvinul® T 150-/Uvinul® A Plus-Containing Dry PowderHaving an Active Ingredient Content of About 20% by Weight

a) Preparation of the Aqueous Dispersion

12.5 g of Uvinul® T 150 and 12.5 g of Uvinul® A Plus were dissolved in216 g of an azeotropic mixture of acetone and water (88/12, v/v) at 70°C. to give a molecularly disperse solution. To precipitate out theactive ingredients in colloidally disperse form, the solution was passedat 240° C. to a mixing chamber, where it was mixed with an aqueoussolution of 45 g of HiCap in 1455 ml of demineralized water. The entireprocess was carried out with a pressure limit of 40 bar in order toprevent evaporation of the solvent. After mixing, a colloidally disperseUvinul® T 150/Uvinul® A Plus dispersion with a pale yellow/cloudy colorwas obtained. Fraunhofer diffraction was used to determine the averagevolume distribution as D (4.3)=0.52 μm with a fines content of thedistribution of 87.5% <1.22 μm.

b) Preparation of a Uvinul® T 150/Uvinul® A Plus-Containing Aqueous DryPowder

Spray-drying the dispersion resulted in a dry powder having an activeingredient content of 10.5% by weight of Uvinul® T 150 and 10.5% byweight of Uvinul® A

Plus (content determination by means of UV/VIS spectroscopy). The drypowder could be redispersed in demineralized water again to form a whitecloudy dispersion (hydrosol).

Fraunhofer diffraction was used to determine the average volumedistribution in the redispersion as D (4.3)=0.9 μm with a fines contentof the distribution of 74% <1.22 μm.

Preparations

EXAMPLE 2 Lip Care Composition

Mass Content (% by Weight) ad 100 Eucerinum anhydricum 10.00  Glycerol10.00  Titanium dioxide, micronized 5.00 Uvinul ® T150/Uvinul ® A Plusdry powder from Example 1 8.00 Octyl methoxycinnamate 5.00 Zinc oxide4.00 Castor oil 4.00 Pentaerythritil stearate/caprate/caprylate adipate3.00 Glyceryl stearate SE 2.00 Beeswax 2.00 Microcrystalline wax 2.00Quaternium-18 bentonite 1.50 PEG-45/dodecyl glycol copolymer

EXAMPLE 3 Composition for Sunblock Containing Micropigments

Mass Content (% by Weight) ad 100 Water 10.00  Octyl methoxycinnamate6.00 PEG-7-Hydrogenated castor oil 6.00 Titanium dioxide, micronized5.00 Uvinul ® T150/Uvinul ® A Plus dry powder from Example 1 5.00Mineral oil 5.00 Isoamyl p-methoxycinnamate 5.00 Propylene glycol 3.00Jojoba oil 3.00 4-Methylbenzylidenecamphor 2.00 PEG-45/dodecyl glycolcopolymer 1.00 Dimethicone 0.50 PEG-40 hydrogenated castor oil 0.50Tocopheryl acetate 0.50 Phenoxyethanol 0.20 EDTA

EXAMPLE 4 Grease-Free Gel

Mass Content (% by Weight) ad 100 Water 8.00 Octyl methoxycinnamate 7.00Titanium dioxide, micronized 5.00 Uvinul ® T150/Uvinul ® A Plus drypowder from Example 1 5.00 Glycerol 5.00 PEG-25 PABA 1.004-Methylbenzylidenecamphor 0.40 Acrylates C₁₀-C₃₀ alkyl acrylatecrosspolymer 0.30 Imidazolidinylurea 0.25 Hydroxyethylcellulose 0.25Sodium methylparaben 0.20 Disodium EDTA 0.15 Fragrance 0.15 Sodiumpropylparaben 0.10 Sodium hydroxide

EXAMPLE 5 Suncream (SPF 20)

Mass Content (% by Weight) ad 100 Water 8.00 Octyl methoxycinnamate 8.00Titanium dioxide, micronized 6.00 PEG-7-Hydrogenated castor oil 5.00Uvinul ® T150/Uvinul ® A Plus dry powder from Example 1 6.00 Mineral oil5.00 Isopropyl palmitate 0.30 Imidazolidinylurea 3.00 Jojoba oil 2.00PEG-45/Dodecyl glycol copolymer 1.00 4-Methylbenzylidenecamphor 0.60Magnesium stearate 0.50 Tocopheryl acetate 0.25 Methylparaben 0.20Disodium EDTA 0.15 Propylparaben

EXAMPLE 6 Water-Resistant Suncream

Mass Content (% by Weight) ad 100 Water 8.00 Octyl methoxycinnamate 5.00PEG-7-Hydrogenated castor oil 5.00 Propylene glycol 4.00 Isopropylpalmitate 4.00 Caprylic/capric triglyceride 5.00 Uvinul ® T150/Uvinul ®A Plus dry powder from Example 1 4.00 Glycerol 3.00 Jojoba oil 2.004-Methylbenzylidenecamphor 2.00 Titanium dioxide, micronized 1.50PEG-45/dodecyl glycol copolymer 1.50 Dimethicone 0.70 Magnesium sulfate0.50 Magnesium stearate 0.15 Fragrance

EXAMPLE 7 Sun Milk (SPF 6)

Mass content (% by Weight) ad 100 Water 10.00  Mineral oil 6.00PEG-7-Hydrogenated castor oil 5.00 Isopropyl palmitate 3.50 Octylmethoxycinnamate 5.00 Uvinul ® T150/Uvinul ® A Plus dry powder fromExample 1 3.00 Caprylic/capric triglyceride 3.00 Jojoba oil 2.00PEG-45/dodecyl glycol copolymer 0.70 Magnesium sulfate 0.60 Magnesiumstearate 0.50 Tocopheryl acetate 3.00 Glycerol 0.25 Methylparaben 0.15Propylparaben 0.05 Tocopherol

EXAMPLE 8 Day Lotion with UV Protection

Mass Content (% by Weight) ad 100 Water 2.00 Cetearyl alcohol 1.00Glycerol monostearate 2.00 Vaseline 7.50 Octyl methoxycinnamate 4.00Octyl salicylate 3.00 Uvinul ® T150/Uvinul ® A Plus dry powder fromExample 1 1.50 4-tert-Butyl-4′-methoxydibenzoylmethane 0.50 Propyleneglycol 0.20 EDTA 0.20 Carbomer 5.00 C₁₂-C₁₅ Alkyl benzoate 0.27Triethanolamine 1.00 Tocopheryl acetate q.s. Fragrance

EXAMPLE 9 Day Cream with UV Protection

Mass Content (% by Weight) ad 100 Water 2.00 Cetearyl alcohol 2.00 Cetylalcohol 1.00 Glycerol monostearate 2.00 Vaseline 7.50 Octylmethoxycinnamate 4.00 Octyl salicylate 3.00 Uvinul ® T150/Uvinul ® APlus dry powder from Example 1 1.504-tert-Butyl-4′-methoxydibenzoylmethane 4.00 Propylene glycol 0.20 EDTA0.20 Carbomer 0.20 Xanthan 0.20 C₁₀-C₃₀ Alkyl acrylate crosspolymer 5.00C₂-C₁₅ Alkyl benzoate 0.54 Triethanolamine 1.00 Tocopheryl acetate q.s.Fragrance q.s. Preservative

EXAMPLE 10 Liquid Make Up

Mass Content (% by Weight) ad 100 Water 2.00 Cetearyl alcohol 2.00Ceteareth 25 6.00 Glycerol monostearate 1.00 Cetyl alcohol 8.00 Paraffinoil 7.00 Cetearyl octanoate 0.2  Dimethicone 3.00 Propylene glycol 1.00Panthenol 3.00 Uvinul ® T150/Uvinul ® A Plus dry powder from Example 11.50 4-tert-Butyl-4′-methoxydibenzoylmethane 3.50 Octyl methoxycinnamate0.1  Bisabolol 5.70 Titanium dioxide 1.10 Iron oxide q.s. Fragrance

EXAMPLE 11 Hair Gel with Sun Protection

Mass Content (% by Weight) ad 100 Water 1.20 Carbomer 0.50Hydroxyethylcellulose 4.00 Triethanolamine 0.70 PEG-40 Hydrogenatedcastor oil 1.50 Uvinul ® T150/Uvinul ® A Plus dry powder from Example 10.70 4-tert-Butyl-4′-methoxydibenzoylmethane 2.80 Octyl methoxycinnamate5.00 Propylene glycol 0.01 EDTA q.s. Fragrance q.s. Sicovit Patent Blue85 E 131

1. A method of producing a powdered preparation comprising2,4,6-trianilino-p-(carbo-2′-ethylhexyl-11′-oxy)-1,3,5-triazine offormula I

and diethylamino hydroxybenzoyl hexyl benzoate of the formula II

the method comprising: a) jointly dispersing the compounds of formula Iand of formula II in an aqueous molecularly disperse or colloidallydisperse solution of a protective colloid; and b) converting thedispersion obtained into a dry powder by removing the water and drying, wherein the protective colloid used in process step a) is modifiedstarch.
 2. The method according to claim 1, wherein the dispersion instage a) comprises the following steps: a₁) dissolving the compounds offormula I and of formula II in one or more water-miscible organicsolvent(s) or in a mixture of water and one or more water-miscibleorganic solvent(s); or a₂) dissolving the compounds I and II in one ormore water-immiscible organic solvent(s); and a₃) mixing the solutionobtained after a₁) or a₂) with an aqueous molecularly disperse orcolloidally disperse solution of modified starch, where the hydrophobicphase of the compounds of formula I and of formula II is formed asnanodisperse phase.
 3. The method according to claim 1, wherein thedrying in process step b) is conducted in the presence of a coatingmaterial.
 4. The method according to claim 1, wherein the jointlydispering of the compounds of formula I and of formula II in an aqueousmolecularly disperse or colloidally disperse solution of includes apreparation of a suspension with the modified starch.
 5. The methodaccording to claim 4, further comprising grinding the suspension priorto conversion into a dry powder.
 6. The method according to claim 4,wherein a₁) the compounds of formula I and of formula II are dissolvedin acetone or isopropanol, or a mixture of water and acetone, or waterand isopropanol at temperatures from 50 to 240° C., a₃) the solutionobtained is mixed with an aqueous molecularly disperse or colloidallydisperse solution of modified starch at temperatures from 25 to 120° C.and b) the suspension formed is spray-dried after removing the organicsolvent.
 7. The method according to claim 1, wherein the jointlydispersing of the compounds of formula I and of formula II in an aqueousmolecularly disperse or colloidally disperse solution includes apreparation of an emulsion with the modified starch.
 8. The methodaccording to claim 1, wherein the protective colloid used is octenylsuccinate starch.
 9. A powdered preparation of a mixture of2,4,6-trianilino-p-(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine of theformula I and diethylamino hydroxybenzoyl hexyl benzoate of the formulaII obtainable by a method according to claim
 1. 10. The preparationaccording to claim 9 with a content of triazine I and benzoyl benzoateII of from 0.1 to 70% by weight.
 11. The preparation according to claim9, comprising one part by weight of triazine I, 0.1 to 10 parts byweight of benzoyl benzoate II.
 12. The use of the powdered preparationdefined according to claim 10 as a photostable UV filter in cosmetic anddermatological preparations.
 13. The method according to claim 1,wherein the molecularly disperse or colloidally disperse solutionincludes one or more organic solvents, which are removed in theconversion to the dry powder.
 14. The method according to claim 4,wherein the protective colloid used is octenyl succinate starch.
 15. Themethod according to claim 7, wherein the protective colloid used isoctenyl succinate starch.
 16. A powdered preparation of a mixture of2,4,6-trianilino-p-(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine of theformula I and diethylamino hydroxybenzoyl hexyl benzoate of the formulaII obtained by a method according to claim
 4. 17. A powdered preparationof a mixture of2,4,6-trianilino-p-(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazine of theformula I and diethylamino hydroxybenzoyl hexyl benzoate of the formulaII obtained by a method according to claim
 7. 18. A powdered preparationcomprising 2,4,6-trianilino-p(carbo-2′-ethylhexyl-1′-oxy)-1,3,5-triazineof the formula I

and diethylamino hydroxybenzoyl hexyl benzoate of the formula II

the preparation prepared by a process comprising: a) jointly dispersingthe compounds I and II in an aqueous molecularly disperse or colloidallydisperse solution of a protective colloid; and b) converting thedispersion obtained into a dry powder by removing the water and drying,and the protective colloid used in process step a) is modified starch,wherein the powdered preparation is used as a photostable UV filter in adermatological preparation.
 19. The preparation according to claim 17,wherein the powdered preparation is present from 5% to 25% by weight inthe dermatological preparation, based on the dry weight of thedermatological preparation.
 20. The method according to claim 2, whereinthe average particle size of the nanodisperse phase is from 0.05 μm to20 μm.
 21. The preparation according to claim 18, wherein themolecularly disperse or colloidally disperse solution includes ahydrophobic phase of the compounds of formula I and compounds of formulaII as a nanodisperse phase, wherein the average particle size of thenanodisperse phase is from 0.05 μm to 20 μm.